Plastic reaction products of sulfur mono-chloride with wax-substituted aromatic compounds



' around 300 or higher. statistically, is of about 24 carbon atoms andPatented Feb. 18, 1941 UNITED STATES PATENT OFFICE PLASTIC REACTIONPRODUCTS OF SULFUR MONO CHLORIDE WITH WAX SUBSTI- I TUTED AROMATICCOMPOUNDS Orland M. Relfl, Woodbury, N. 1., assignor to Socony-VacuumOil Company, Incorporated, a I corporation of New York I. No Drawing.Original application August .6, 1942, Serial No. 453,847. Divided andthis application July 21, 1944, Serial No. 546,062

This invention has reference to novel compositions of matter-havingrubber-like properties produced by the action of valclehydes, aldehydeamines, halides of sulfur and other agents, known to have the effect ofresinifying phenols, on

poly-arylated petroleum waxes and the like wherein the substituent arylgroups are in the nature of phenols. This application is a division ofmy copending application Serial No. 453,847,

filed August 6, 1942.

1 The techniques for resinification of phenols with a wide variety ofresinifying agents to pro-- I duce hard, brittle resins are well known,and a' large number of types of such products have been produced and arein wide use. casesythe aromatic body is substituted by alkyl 1 In many 4Claims. (c1. 260-48) 2 the proportion of constituents having less thancarbon atoms is very minor. In general, aliphatics from any source maybe employed' provided they are predominantly straight-chain compounds ofpredominantly at least 20 carbon atoms.

The aliphatic hydrocarbons are condensed with hydroxyaromatic'compoundsto produce the poly arylated aliphatics.

groups but in all such instances, the aromatic reactant has beencharacterized by a molecule having a single aryl nucleus. I have nowfound that resilient masses having extremely high re- -.sistance toshock may be prepared by reactions paralleling the known resiniflcationsnoted above,

but differing therefrom in that the raw material employed is derivedfrom petroleum wax or the like which has'been poly-arylated withphenols.

As will be apparent from the detailed discussion hereinafter, theintermediate normally includes aromatic nuclei which are substituted ata plurality of points by alkyl groups. However. since the average alkylgroup-bears a number .of aryl substituents, and in order .to clearlypoint out the different nature of this raw material, it will be referredto herein as poly-aryl aliphatic.

Many of the present products strongly resemble rubber in its more usualcommercial'forms having substantial elasticity, tensile strength, etc.All of the products may be said to be "rubber-like? in that theyresemble some form of rubber. Certain preferred forms have somewhattheappear .ance and properties of.such rubber forms as ebonite. .The key tothe properties obtained according to this invention'lies in the natureof the aliphatic portion of the molecule of the polyaryl aliphatic andthe degree of its substitution with aryl nuclei of the type specified.The aliphatlc is typified by alkyl groups derived from petroleum wax.This is a mixture of straightchain aliphatic hydrocarbons of relativelyhigh molecular weight, the molecular weight averaging The averagemolecule.

the mixture is predominantly made up of molecules of at least 20 carbonatoms. Some petroleum waxes are reported to include aliphatichydrocarbons oi as few'as 15 carbon atoms, but

The. hydroxyaromatic compounds which may be used in the practice of myinvention are phenols, thatis, they are aromatic compounds which have atleast one hydroxyl group attached directly to a carbon ring and may beeither monoor polynuclear phenols. To more clearly describe thehydroxyaromatic compounds with which this invention is concerned, I maysay that the compounds are of the following general formulae:

a n R it I a a a BQ b a a, (c) a a I v v I R a a R i R R wherein atleast one B. represents a hydroxy group 7 and the remaining R's may beselectedfrom the group of radicals comprising hydrogen, hydroxy, alkyl,aryl, aralkyl, aikoxy or aroxy. As examples of hydroxyaromatic compoundsof the group -above deflned, I may name phenol, resorcinol,hydroquinone. catechol,

phenyl, benzyl phenol, phenyl ethyl phenol,

xylenol, hydroxy-dimethyl hydroxy-diphenyl, ethyl hydroxy-diphenyl,guaiacol, the mono-ethylethc-r oi catechol, alphaand beta-naphthol,alphaand betamethyl naphthol, phenyl naphthol, tolyl naphthol,

" xylyl naphthol, benzyl naphthol, mono-methylether ofdihydroxynaphthalene, anthranol, phenyl methyl anthranol, and the like.Because of their tendency to re-arrange in the Friedel-Crafts reactionto form hydroxy-arylated waxes, the

' mixed aryl-aliphatic-ethers, such as anisol and alkyl-ethers ofnaphthols, may also be used.

' tions.

poly-aryl aliphatic may anem c be accomplished in any suitable manner,the invention may well. be considered by reference to the classicFriedel-Craftssynthesis as exemplary. Such preparation is preferredbecause of the control it affords over V hydrocarbons of predominantlystraight-chain structure and predominantly at least 20 carbon atoms, achlorinated wax and aphenol are reacted to produce a poly-arylated waxin. which each waxradical is linked to at least 2 aryl radicals. Inorder to achieve .poly-arylation, it is of course necessary that thechlorwax be at least di-chlorinated. Eighteen per cent chlorine seemsthe lower limit for obtaining final products having sufiicient toughnessand tensile strength to be of value as rubber-like composi-- It willberecognized that the mixture of chlorwax'will contain some trichlorwaxand some mono-chlorwax. However, if the proportion of chlorinecorresponds substantially to that in the dichlor derivative, the productobtained is substantially the same as that from pure dichlor wax.

ated wax is of a much more complex structure than indicated by the term:diaryl wax. The polyaryl waxes up to tetra-aryl may be used to obtainthe advantages of the invention, corresponding to Friedel-Craftsproducts from v,chlorwaxes of about 18% to about 30% chlorine content.Preferably, used, for example, those derived by reaction with.

tri-aryl derivatives are chlorwax of about 25% chlorine content.

The proportion of aromatic reactant to combined' chlorine in theFriedel-Craits reactionis important. as a governing factor in the degreeof resilience. This determines the average number of points at whicheach aryl nucleus will be substituted by an alkyl group. For generalconsiderations, this ratio must be based on the chlorine my; But: all,even these latter gummy substances, exhibit a characteristic conchoidalfracture and resinous luster. at a fracture surface.

The chemical nature of the poly-arylated waxes are, as might beexpected, widely varied and extremely complex. A composition derivedfrom phenol and 27 chlorwax (petroleum wax chlorinated to 27%chlorinecontent) in proportions to theoretically tri-alkylate the phenolcontains about phenol, with the remainder of the molecule consisting ofcombined wax radicals. The poly-arylated waxes may be represented by thegeneral formulae as set out below,

it being understood that these merely represent probable linkages. Itis'not attempted to accurately depict molecules actually occurring, inthe complex compositions, since these vary widely and very likelyincludein a single molecule several of the linkages indicated below. Forsimplicity, the aromatic nuclei are represented uniformly by the phenylradical.

in the chlorwax since it is this molar ratio rather than that based onmols of--wax which governs resilience. The compositions with which thisinvention is concerned are prepared from poly-aryl waxes and the like inwhich the average aryl nucleus is substituted at "from 2 to 4 points;that is, an intermediate prepared by the i three mols of combinedchlorine willbe designated hereinafter as "wax-phenol (3-27) withcorresponding nomenclature for other poly-arylated waxes; the firstfigurein the parentheses denoting the molar ratio of combined chlorineto aromatic and the second referring to chlorine content of the chlorwaxused.

The poly-arylated waxes used in accordance ity. Those prepared from thechlorwaxes of lower chlorine content may be somewhat gum- "With theinvention are solids of varying elastic- The compositions arerepresented in the foregoing formula with a single attachment of thearomatic group to each wax group, but in the reaction of chlorwax ofhigher chlorine .content with aromatic compounds, apparently thearomatic group will be attached in some cases to 1 more than one carbonof the same wax group,

particularly. in reactions with aromatic com-- pounds of the condensednuclei and polycyclic ype. 7 Some chain formation would be expected tooccur in the reaction of aromatic compounds with chlorinated waxes, inwhich' case-the following representation would be applicable,representing a continuation of the chain structure.

resented in the foregoing formulae as di-substituted aromatic,compounds, but an amount of chlorwax can be reacted with the aromaticcompounds sufficient to substitute all the replaceable hydrogens of thearomatic nucleus. Generally, an amount of chlorwax sumcient totrisubstitute the aromatic compound is favored.

Example I A suitable poly-arylated wax is obtained by reaction of 48grams of phenol with 200 grams of chlorwaxcontaining 27% chlorine byweight in the presence of 3 grams of anhydrous aluminum chloride.

Paraflin wax of A. S. T. M, melting point of about 126 F. and'of averagemolecular weight of about 350, is melted and a current of chlorineintroduced at a temperature of about 200 F. until 7 the mass containsabout 27% by weight of chlorine. The phenol is then introduced, followedby gradual addition of the anhydrous A101: at a.

The poly-arylated wax compositions are reptemperature of about 150.T'l'ie temperature of the mixture is gradually F. with rapid stirring.

raised to about 350 F. during a two-hour period,

, with efficient stirring to reduce foaming caused by evolution of HClgas. The reaction mixture is held at this temperature until theevolution of HCl is completed, which will require about one hour. Thereaction mixture is then cooled and contacted with water to decomposethe.alumi-\ num chloride reaction product, whereby thealuminum chloridecan be removed from the mixture. To insure removal of corrosive halogen,the product is then digested with dilute (1%) caustic soda by refluxingthe mixture several hours, folf Example II Wax phenol (3-30) issimilarly prepared from 600 parts of chlorwax' of 30% chlorine content,159 parts of phenol and 12 parts of aluminum chloride.

Example III Poly-arylated waxes from chlorwax of lower chlorine contentare also readily prepared. For example, 4,540 parts by weight of 18%chlorwax, 721 parts of phenol and 180 parts of aluminum chloride wereused in preparing wax phenol (3-18).

having a reactive methylene group are very effective. Further, suitabletreating agents include broadly, aldehydes, ketones, alcohols andhalogenated hydrocarbons. Accordingly, for the purposes of thisinvention, the following compounds might be mentioned as illustrative ofthe resinifying agents that may be used. Aliphatic aldehydes, such asformaldehyde and its equivalent derivatives as typified byhexamethylene-tetramine and trioxy-methylene; also acetaldehyde,propylaldehyde, butyraldehyde and higher homologous aldehydes; keton-essuch as acetone, methyl ethyl ketone, diethyl ketone, ethyl propylketone and the like; monovalent alcohols and polyvalent alcohols, suchas benzyl alcohol, glycol, ethylene glycol, and glycerine; and thoseresinifying agents which eliminate halogen hydrides in reaction with theabove-mentioned hydroxyaromatic hydrocarbons as typified by halogenatedaryl hydrocarbons, for example, benzyl chloride, chlor-naphthalene andchlor-anthracene.

Other suitable treating agents, as described in my prior applicationSerial No. 187,676, filed January 29, 1938, are sulfur reagents such aselementary sulfur and sulfur chlorides (e. g., sulfur mono-chloride) andoxidizing agents such as oxy gen and potassium permanganate.

In this Friedel-Crafts reaction, the-chlorwax and hydroxyaromaticcompound are mixed to-- gether at a temperature slightly above themelting point of the wax (in the present instance, under 150 F.),thereafter adding the aluminum chloride catalyst slowly in order toavoid excessive foaming due to evolution of hydrochloric acid gas.

The reaction rate is controlled by regulating the temperature. Using 2%aluminum chloride with respect to chlorwax, some reaction takes placearound 140 F., but a steady rapid evolution of HCl gas is obtainedaround 200 F. The

reaction may be carried out suitably by heating the reaction mixture to200 F., then gradually raising the temperature during a two-hour periodto 350 F. to complete the reaction. As the reaction proceeds, themixture becomes more viscous, but by graduall raising the'temperature, I

the viscosity of the mixture is sufficiently reduced,

so that diluents are unnecessary to give proper mixing.

Example I V Wax beta-naphthol (3-20) is similarly prepared from 800parts of 20% chlorwax, 216.3 parts of beta-naphthol and 24 parts ofaluminum chloride.

To obtain the desired product of the invention, the polyarylated waxesare treated with a resinifying agent, i. e., a composition adapted toresinify phenols. 187,677, filed January 29, 1938, of which my saidapplication Serial No. 453,847 is a continuationin-part, I havedisclosed a number ofsuch treating agents. Of the known materials forresinifying phenols, I prefer to use hexamethylene-tetramine orformaldehyde in acid medium; or sul- The said prior applications arecontinuationsin-part of my earlier application Serial 'No. 18,342, filedApril 26, 1935.

One novel aspect of this invention is in the small amounts ofresinifying agents required for formation of atougher product. This isdue to the complexity of the products wherein more than one aryl groupis present per molecule as described in the foregoing. In theresinification of phenols in prior art, an amount of resinlfying, agentequivalent to the phenol was necessa y.- while only a fraction of thisamount is required for the poly-arylated wax compounds. The rea+ son forthis will be clear by examining the representative formulae of column 4.For instance} it is apparent that a single molecule of formalde-i hydecould join two molecules of the poly arylated\ compound by reacting witha single phenol substituent of each molecule. In other words, the

- quantity of hexamethylene-tetramlne under gthe pressure developed inthe reaction at a tempera: ture of 300 F. The reaction may also becarried out in open vessels at atmospheric pressure, by addinghexamethylene-tetramine at intervals with stirring. After about 2 hours,the mixt e converts to a rubber-like mass. 1

Reactions of the poly-arylated waxes with trioxy-methyle'ne are suitablyconducted at about 200? F. in the presence of about 2% hydrochlokicacid. Similarly,.butyraldehyde and glycerol may In my prior applicationSerial No.

be used at about 300 F.'us ing 2% acid catalyst, hydrochloricandsulfurlc, respectively. 1

Example VI reactant.

Example VII A sampleof the highly viscous wax beta naphthol (3-20) ofExample IV was mixed with 2% by weight of hexamethylene-tetramine andheated at 150 C. for 2 hours at which time it had converted to-arubber-like mass.

Example vm A sample of wax-substituted phenol (3-27) Example I was mixedwith 2% by weight of hexamethylene-tetramine on a rubber mill and thenheated in a mold at 180- C. for one hour. A tough, rubber-likecomposition of good flexibility and high resistance to flow underpressure was formed. 1

Example IX AF'riedel-Crafts reaction product formed as in Example 11 waswater-washed without any treatment with dilute caustic to removeunreacted phenol and then reacted with 30 grams of 37% solution offormaldehyde in the presence of 18 cc. of 2% HCl for one hour. Theproduct was then water-washed and dried on a rubber mill. This productwas then milled with 2% by weight of hexamethylene-tetramine and heatedin a mold at 150 C. for one-half hour. Thi product was harder than thatof Example VIII but still had high resistance to shock withoutincorporating fillers ordinarily used for this purpose.

Iclaim: I v 1. A resilient composition of matter formed by heatingchlorinated petroleum wax of at least 18% chlorine content with a.phenol having as sole nuclear substituents radicals from the classconsisting of hydrogen, hydroxy, alkyl, aryl, aralkyl and alkoxy, in thepresence of a Friedel- Crafts catalyst, and in a molar ratio of combinedchlorine to phenol of;not less 2 or more than 4 to produce acondensation product and in which, on the average, more than one arylnucleus is attached to each wax radical and each arylnucleus issubstituted by wax radicals at from 2 to 4 points, and thereafterheating: said condensation products with sulphur monochloride to reactthe same.

2. A resilient composition or matter formed by heating chlorinatedpetroleum wax of 18% to 30% chlorine content with a phenol having-assole nuclear substituents radicals from the class consisting ofhydrogen, hydroxy, alkyl, aryl, aralkyl and alkoxy, in the presence of aFriedel- Crafts catalyst, and in a molar ratio of combined chlorine tophenolof not less than 2 or more than 4 to produce a condensationproduct and in which, on the average, more than one aryl nucleus isattached to each wax radical and each aryl nucleus is substituted by waxradicals at from 2 to '4 points, and thereafter heating saidcondensation products with, sulphur monochloride to react the same.

- 3. A resilient composition of matter formed by heating chlorinatedpetroleum wax of about 25% chlorine content with a phenol having as solenuclear substituents radicals from the class consisting of hydrogen,hydroxy, alkyl, aryl, aralkyl and alkoxy, in the. presence of aFriedel-Crafts catalyst, and in a molar ratio of combined chlorine tophenol of not less than 2 or more than 4 to produce a condensationproduct and in which, on the average, more than one aryl nucleus isattached to each wax radical and each aryl nucleus is substituted by waxradicals at from 2 to 4 points, and thereafter heating said condensationproducts with sulphur monochloride to react the same.

4. A resilient composition of matter formed by heating chlorinatedpetroleum wax of at least 18% chlorine content with phenol, in thepresmonochloride to react the same.

QRLAND M, REIFF.

REFERENCES CITED The following references are of record in the me ofthis patent:

' g I UNITED STATES PATENTS Number Name Date 2,178,571 Flett Nov. 7,1939 2,134,547 Buc Oct. 25, 1938 2,139,321 Mikeska et a1 Dec. 6, 1938Ellis Mar. 20, 1928

